CN102884100B - Include the composition epoxy resin of poly- (expoxy propane) polyalcohol as toughener - Google Patents
Include the composition epoxy resin of poly- (expoxy propane) polyalcohol as toughener Download PDFInfo
- Publication number
- CN102884100B CN102884100B CN201180020459.2A CN201180020459A CN102884100B CN 102884100 B CN102884100 B CN 102884100B CN 201180020459 A CN201180020459 A CN 201180020459A CN 102884100 B CN102884100 B CN 102884100B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- composition
- toughener
- polyalcohol
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Abstract
Curable composition epoxy resin, it includes (a) at least one epoxy resin；(b) at least one curing agent；At least one high-molecular-weight poly (expoxy propane) polyalcohol toughener (c)；With the method for preparing the curable composition epoxy resin.
Description
Background of invention
Invention field
The present invention relates to the toughener for composition epoxy resin；More particularly, the present invention relate to asphalt mixtures modified by epoxy resin
High-molecular-weight poly (expoxy propane) polyalcohol toughener in oil/fat composition.
Background and description of related art
Have various hot come flexibilizing epoxy for example by the use of core shell rubber as toughener by the use of many existing known toughener
The known method of thermoset material.In another example, United States Patent (USP) No.4,497,945 disclose using low molecule amount
The toughener of (1000-3000 dalton) poly- (expoxy propane) glycol or triol as epoxy-anhydride thermosets.It is above-mentioned existing
There are known low molecular weight polyols in technology that there is lacking for the glass transition temperature (Tg) for the thermosetting system for reducing gained
Point.
Therefore need to provide and (1) is improved into epoxy with the curable epoxy system with toughener, the toughener
The toughness of resin system, but do not reduce or negatively affect the final thermosets made of the epoxy-resin systems
Tg；(2) property of final thermosetting system can not adversely be influenceed.
Summary of the invention
The present invention relates to for example poly- (expoxy propane) polyalcohol of high molecular weight polyols as toughener in flexibilizing epoxy tree
Answering in some machineries and thermal properties such as Tg of the oil/fat composition such as epoxy resin-anhydride system without damaging thermosets
With.
Advantageously, high-molecular-weight poly (expoxy propane) polyalcohol is used in curable epoxy system, there is provided tough
Property improve but without sacrifice obtained by thermosetting system final Tg thermoset articles.
One embodiment of the present invention is related to curable resin combination or system (or preparation), and it includes (a) extremely
A kind of few epoxy resin；(b) at least one curing agent；At least one high-molecular-weight poly (expoxy propane) polyalcohol toughness reinforcing (c)
Agent；The number-average molecular weight of wherein described toughener is greater than about 7000.
An advantage using the toughener of the present invention includes, for example, wherein described toughener provides and shows Tg not
The composition epoxy resin of change；Wherein Tg's may range from 70 DEG C to 265 DEG C.In addition, the toughener of the present invention increases with business
Tough dose compares as carboxylic acid-terminated hycar (CTBN), has relatively low viscosity.
Brief description of the drawings
In order to illustrate the present invention, accompanying drawing shows currently preferred form of the present invention.It should be appreciated, however, that the present invention is not
It is confined to the embodiment shown in accompanying drawing.
Fig. 1 is showing when using the toughener of embodiment 1, control and Comparative examples A, and molecular weight is relative to thermosetting material
The Tg's of material illustrates.
Detailed description of the invention
The broad aspect of the present invention includes curable composition epoxy resin, system or preparation, and it includes (a) extremely
A kind of few epoxy resin；(b) at least one curing agent；At least one high-molecular-weight poly (expoxy propane) polyalcohol toughness reinforcing (c)
Agent and (d) optionally at least one catalyst.
On " HMW (MW) " of the present composition herein, refer to the greater than about 7000 equal MW of number.For example,
In one embodiment, the MW of the present composition can be about 7000 to about 20,000.
The curable compositions of the present invention include at least one epoxy resin, component (a).Epoxy resin be those contain to
The compound of few vicinal (vicinal) epoxy radicals.Epoxy resin can be saturated or unsaturated, aliphatic, cyclic aliphatic,
Aromatic series or heterocycle, and can be substituted.The epoxy resin can also be monomer or polymerization.Available for the present invention
Itemizing for epoxy resin see Lee, H. and Neville, K., " epoxy resin handbook (Handbook of Epoxy
Resins), " McGraw-Hill Book Company, New York, the 1967, the 2nd chapter, 257-307 pages；Pass through reference herein
It is incorporated into herein.
Being used as the epoxy resin of the component (a) of the present invention in embodiment disclosed herein can change, and including conventional
With commercially available epoxy resin, they being applied in combination individually or with two or more.It is used in selection public herein
During the epoxy resin for the composition opened, the property of final products is not only considered, and be also contemplated that described in viscosity and possible influence
Other properties of resin combination processing.
Particularly suitable epoxy resin well known by persons skilled in the art is based on polyfunctional alcohol, phenol, cycloaliphatic carboxylic acid, virtue
The reaction product of fragrant amine or amino phenols and epichlorohydrin.Some non-limiting embodiments include, for example, bisphenol-A 2-glycidyl
Ether, Bisphenol F diglycidyl ether, the triglycidyl ether of resorcinolformaldehyde resin and p-aminophenol.Art technology
Other suitable epoxy resin known to personnel include epichlorohydrin respectively with o-cresol phenolic resin and linear phenol-aldehyde resin
Reaction product.It is also possible that the mixture with two or more epoxy resin.
Available for the present invention to prepare the epoxy resin of curable compositions, component (a), commercially available prod can be selected from.Example
Such as, the D.E.R for being available from The Dow Chemical Company can be used331、D.E.R.332、D.E.R.334、
D.E.R.580, D.E.N.431, D.E.N.438, D.E.R.736 or D.E.R.732.As illustrating for the present invention, epoxy
Resin Composition (a) can be liquid epoxies, such as D.E.R.383, and it is the diglycidyl ether (DGEBPA) of bisphenol-A,
Epoxide equivalent, viscosity with 175-185 are 9.5Pa-s and density is 1.16 grams/cc.It can be used for the epoxy resin ingredient
Other commercial epoxy resins can be D.E.R.330, D.E.R.354 or D.E.R.332.
Other the suitable epoxy resin that can be used as component (a) are disclosed in, for example, United States Patent (USP) Nos.3,018,262,7,
163,973rd, 6,887,574,6,632,893,6,242,083,7,037,958,6,572,971,6,153,719 and 5,405,
688；PCT Publication WO 2006/052727；U.S. Patent Application Publication Nos.20060293172 and 20050171237；Respectively herein
It is incorporated herein by reference.
In some embodiments, based on epoxy resin composition, cycloaliphatic anhydride curing agent, toughener and catalyst
Gross weight, the epoxy resin composition can the curable compositions about 10 percentage by weights (wt%) to about 90wt%
The amount of scope is present in curable compositions.In other embodiments, the scope of epoxy composite is curable compositions
About 15wt% to about 85wt%；In other embodiments, it is about 20wt% to about 80wt%；In other embodiments,
It is about 25wt% to about 75wt%；In other embodiments, it is about 30wt% to about 65wt%；In other embodiments
In, it is about 30wt% to about 60wt%, wherein above-mentioned percentage by weight is hardened based on epoxy resin composition, cycloaliphatic anhydride
The gross weight of agent, toughener and catalyst.
Available for the curing agent (also referred to as curing agent or crosslinking agent) of the curable epoxy resin composition of the present invention, component
(b) cyclic aliphatic and/or aromatic anhydride can, be included；With its mixture.Cycloaliphatic anhydride curing agent can include for example, receiving
Dick (nadic) methyl anhydride, hexahydrophthalic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, first
Base hexahydrophthalic anhydride and their derivative；With its mixture.Aromatic anhydride can include, for example, O-phthalic
Acid anhydrides, trimellitic anhydride and its mixture.Anhydride curing agent can also include styrene and maleic anhydride and such as United States Patent (USP)
No.6, the copolymer of other acid anhydrides described in 613,839, the patent are incorporated herein by reference herein.
Can also be provided in addition to anhydride hardener described above, in curable composition additional curing agent or
Curing agent forms polymer composition to promote the crosslinking of composition epoxy resin.As epoxy resin, additional hardening
Agent and curing agent can use using used aloned or as the mixture of two or more curing agent.The curing agent component can be with
Including there is any compound of the active group of reactivity with the epoxy radicals with epoxy resin.Curing agent can include nitrogen
Compound such as amine and their derivative；For example carboxylic acid-terminated polyester of oxygenatedchemicals, linear phenol-aldehyde resin, bisphenol-A line style
It is novolaks, DCPD- phenol condensation products, bromination phenolic aldehyde (phenolic) oligomer, amino-formaldehyde condensation product, phenol, double
Phenol A and cresol novalac, the epoxy resin of phenolic aldehyde end-blocking；Sulfur-containing compound such as polythiaether, polymercaptan；With its mixing
Thing.
Example available for the curing agent of the present invention can include being known to be used in appointing for cured epoxy resin based composition and use thereof in packaging
What catalytic curing material.Suitable catalytic curing agent include tertiary amine, quaternary ammonium halide, lewis acid such as boron trifluoride and its
Any combinations etc..
In some embodiments, based on epoxy resin composition, cycloaliphatic anhydride curing agent, toughener and catalyst
Gross weight, the mixture of the cycloaliphatic anhydride curing agent or cycloaliphatic anhydride curing agent can the curable compositions pact
10wt% is present in curable compositions to the amount about in the range of 90wt%.In other embodiments, cycloaliphatic anhydride is hard
The about 15wt% for being generally in the range of curable compositions to about 85wt% of agent；In other embodiments, it is preferably from about
20wt% to about 80wt%；In other embodiments, even more preferably about 25wt% to about 75wt%；In other embodiment
In, more preferably about 30wt% to about 65wt%；In other implementations, most preferably about 35wt% is to about
60wt%, wherein above-mentioned percentage by weight is to be based on epoxy resin composition, cycloaliphatic anhydride curing agent, toughener and catalyst
Gross weight.
The composition epoxy resin of the present invention includes toughener, and it is for example poly- that the toughener includes high molecular weight polyols
(expoxy propane) polyalcohol is with composition epoxy resin described in toughness reinforcing (such as epoxy resin-anhydride system) without damaging thermosetting
The some machineries and thermal property of material, such as glass transition temperature.Available for poly- (expoxy propane) polyalcohol of the invention
Example can include the polyalcohol with following chemical constitution：
Generally, the number-average molecular weight available for the toughener of the present invention is greater than about 7,000 to about 20,000, preferably from about 8,
000 to about 16,000, more preferably from about 8,000 to about 15,000.The molecular weight of the toughener should cause final composition to have
There is the property of balance, for example, wherein final thermosets product shows the fracture toughness of enhancing but without described in sacrifice
The Tg of final thermosets product.
In some embodiments, toughener can about 0.1wt% be present in the amount of about 50wt% scope it is curable
Composition in.In other embodiments, the scope for the amount that the toughener may have is about 0.2wt% to about
40wt%；It is about 0.5wt% to about 30wt% in other embodiments；It is about 1wt% in other implementations to about
The gross weight of 25wt%, wherein above range based on epoxy resin composition, cycloaliphatic anhydride curing agent, toughener and catalyst
Amount.
In an example of the composition epoxy resin of the present invention, the composition can include optional component, example
Such as optional catalyst, to promote epoxy resin-curing agent to react, particularly for example using anhydride curing agent when.Available for this
The catalyst of invention can include, for example, at least one tertiary amine；At least one imidazoles；At least one quaternary ammonium salt；It is or at least one
Chromium complex；Or its combination.
In some embodiments, catalyst can using scope as 0wt% to about 10wt% or in other embodiments
It is that about 0.01wt% to about 10wt% amount is present in the curable compositions.In other embodiments, the catalysis
Agent can about 0.1wt% to about 8wt% scopes amount exist；It is about 0.5wt% to about 6wt% in other embodiments；
It is about 1wt% to about 4wt% in other embodiments, wherein above range is based on epoxy resin composition, cycloaliphatic anhydride
The gross weight of curing agent, toughener and catalyst.Beyond above-mentioned catalyst concn scope, epoxy resin and anhydride curing agent
Reaction may be slow or may not occurred.
In a kind of embodiment of the composition epoxy resin of the present invention, it is anti-that the composition can include optionally non-
Answering property diluent.Non-reactive diluent available for the present invention can include, for example, it is, in general, that the composition can be with
Include 0wt% to 10wt% non-reactive diluent.In other embodiments, the composition can include about
0.1wt% to about 8wt% non-reactive diluent；In other embodiments, about 0.5wt% to about 8wt% non-reaction
Property diluent；And in other embodiments, about 1wt% to about 8wt% non-reactive diluent.
The present invention it is curable or can thermosetting composition can optionally comprising one or more to their intended purpose
Other useful additives.For example, the optional additive available for the present composition can include, but not limited to stabilization
Agent, surfactant, flow ability modifying agent, pigment or dyestuff, delustering agent, degasser, fire retardant (such as inorganic combustion inhibitor, halogenation
Fire retardant and non-halogenated flame retardent such as phosphorated material), toughener, curing initiator, curing inhibitors, wetting agent, colouring agent
Or pigment, thermoplastic, processing aid, ultraviolet blocking compound, fluorescent chemicals, UV stabilizer, inert filler, fiber
Reinforcing agent, antioxidant, impact modifying agent include thermoplastic particle, and its mixture.It is listed above be intended to it is exemplary and
It is non-limiting.Preferable additives for the preparation of the present invention can be optimized by those of skill in the art.
Gross weight based on curable compositions, in some embodiments, curable compositions can also include 0wt%
To about 50wt% optional additives；In other embodiments, about 0.1wt% to about 50wt% optional additives.At it
In his embodiment, curable compositions can include about 0.1wt% to about 5wt% optional additives；Implement in others
In mode, about 0.5wt% to about 2.5wt% optional additives.
By the way that reactive component above is mixed curable epoxy resin composition of the invention is prepared to realize.For example,
The epoxy resin, the curing agent, the polyalcohol toughener and optional catalyst can be made an addition to reaction vessel
In；Then the component is allowed to be configured to composition epoxy resin.Although the order of mixture is not crucial, i.e. preparation of the invention
Or the component of composition can be mixed with any order to provide the thermosettable composition of the present invention, but in preferred embodiment
In, polyalcohol can be added in anhydride curing agent or epoxy resin-anhydride-cured preparation in.
Any optional various formulation additives above-mentioned, such as filler, can also be during mixing or mixed
Composition is made an addition to before closing, to form said composition.
The all components typical case of the composition epoxy resin can be being prepared with the low viscosity for intended application
Mixed at a temperature of effective composition epoxy resin and scattered.Typically about 0 DEG C of temperature during all components mixing is extremely
About 100 DEG C, and preferably from about 20 DEG C to about 50 DEG C.
Curable compositions can be formed：By (1) aromatic epoxy resin or cycloaliphatic epoxy resin or (a) ring grease
Race's epoxy resin and (b) aromatic epoxy resin cycloaliphatic resin, Epoxy novolac resin, epoxy bisphenol A novolac tree
Fat, polyfunctional epoxy resin, the mixture of bisphenol-A or Bisphenol F base epoxy, increase with (2) cycloaliphatic anhydride curing agent, (3)
Tough dose and (4) optional catalyst combination.As described above, other curing agent, epoxy resin, catalyst, increasing can also be added
Tough dose and other additives.The relative scale of epoxy resin composition and cycloaliphatic anhydride curing agent can be depended in part on and made
The property needed for curable compositions or thermoset composition, the cure response needed for the composition and the combination made
Pot life needed for thing." pot life " refers to that viscosity at service temperatures increases to the initial viscosity of the preparation herein
Twice or three times of the time spent.
The composition epoxy resin prepared by the inventive method is typically about 0.1Pa-s to about in 25 DEG C of range of viscosities
15,000Pa-s。
The curable epoxy preparation or composition of the present invention can be formed by curing thermosetting under Conventional processing conditions
Material.Resulting thermosets shows outstanding heat-mechanical performance, such as good toughness and mechanical strength, together
When keep high heat stability.
Producing the method for the thermoset products of the present invention can be carried out by following manner：Gravity-assist pouring, vacuum casting, automatically
Pressure is gelled (APG), vacuum pressure gelling (VPG), perfusion, filament winding, laying injection, transfer shaping, pre-preg, dipping,
Coating, sprinkling, brush etc..
Cured reaction condition includes, for example, at typically about 0 DEG C to about 300 DEG C；Preferably from about 20 DEG C to about 250 DEG C；With
Under even more preferably about 50 DEG C to about 200 DEG C of temperature range, reaction is performed.
The pressure of curing reaction can be in for example, about 0.01bar to about 1000bar, preferably from about 0.1bar to about
100bar, more preferably from about 0.5bar are to performing under about 10bar pressure.
It is curable or can the solidification of composition of thermosetting can perform the scheduled time for being for example enough to solidify the composition
Section.For example, hardening time can select between about 1 minute to about 24 hours, preferably between about 10 minutes to about 12 hours,
More preferably between about 100 minutes to about 8 hours.
The solidification process of the present invention can be partial or continuous process.During the reactor that uses can be this area
Any reactor and auxiliary equipment known to technical staff.
In one embodiment, curable compositions described above can be arranged on base material and solidify.The base
Material is not particularly limited.Thus, base material can include metal, such as stainless steel, iron, steel, copper, zinc, tin, aluminium, alumite etc.；This
The alloy of metalloid, and it is coated with the sheet material of this metalloid and the laminated plate material of this metalloid.Base material can also include polymer,
Glass and various fibers, for example, carbon graphite；Boron；Quartz；Aluminum oxide；Glass, such as E glass, S glass, S-2 GlassOr
C glass；And the carborundum or silicon carbide fibre of titaniferous.Commercially available fiber can include：Organic fiber, such as DuPont
KEVLARSalic fiber, such as 3M NEXTELFiber；Silicon carbide fibre, such as Nippon Carbon
NICALONWith the TYRRANO of the silicon carbide fibre of titaniferous, such as UbeIn a particular embodiment, it is described curable
Composition can be used for being formed at least a portion of circuit board or printed circuit board.In some embodiments, the base material can
To scribble bulking agent, to improve adhesion of the described curable or solidification composition filling to base material.
Cured product or thermoset products prepared by the composition epoxy resin by solidifying the present invention is advantageously shown
Improved machinability and heat-mechanical performance (such as precuring formulation viscosity, glass transition temperature, modulus and toughness) it is flat
Weighing apparatus.The cured product can be visually transparent or milky.With the similar heat for only using conventional epoxy to prepare
Thermoset material is compared, the fracture toughness increase of the thermosets prepared using epoxy resin of the present invention, without sacrificing gained
Thermosets final Tg.
The Tg of the thermosets product is by depending on the curing agent and epoxy resin that are used in curable compositions.It is logical
Often, the Tg of cured epoxy resin of the invention can be about 100 DEG C to about 300 DEG C, even more preferably about 100 DEG C to about 265 DEG C.
Similarly, the fracture toughness of thermosets product also by depending on the curing agent that is used in curable compositions and
Epoxy resin.Generally, the fracture toughness of cured epoxy resin of the invention can be about 0.4MPa/m1/2To about 3MPa/m1/2, more
Preferably from about 0.6MPa/m1/2To about 2MPa/m1/2。
The composition epoxy resin of the present invention can be used for prepares coating, film, adhesive, laminated material, composite (example
Such as filament winding, pultrusion), the epoxy thermoset material or cured product of the form such as electronic device.In some embodiments
In, pultrusion, filament winding, casting or priming by vacuum are typically preferable.
As the example of the present invention, it is, in general, that composition epoxy resin can be used for casting, embedding, encapsulation, molding and pressure
Type.Made the invention is particularly suited to all types of electroforming, embedding and package application；Molding and plasticity die mould；With manufacture epoxy
Polymer matrix composites part, particularly production pass through the big part of epoxy resin-matrix caused by casting, embedding and encapsulation.Thus produce
Raw composite can be used for some applications, such as application or Electronic Packaging, casting, molding, embedding, encapsulation, note are made in electroforming
Modeling, resin transfer moulding, composite, coating etc..
Embodiment
The present invention is further described in following examples and comparative example, but is not construed as limiting its scope.
Various terms and title used in embodiment include following：" TA " represents toughener；SD-1731 is derived from Hexion
High-purity phenol-formaldehyde novolac varnish；DL-50 is derived from Air Products aromatic amine curing agent；DER 383 is
EEW is 180 and can be the epoxy resin commercially available from Dow Chemical Company；" MTHPA " represents methyl tetrahydrochysene O-phthalic
Acid anhydrides simultaneously derives from what Dixie Chemical were sold with ECA 100 title；Acclaim 8200 is poly- commercially available from Bayer
Homopolymer of propylene oxide；" NMA " represents Na Dike methyl anhydride and derives from Dixie Chemical Company；SYNA EPOXY
21 be 3,4 epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylates, and EEW is 140 and derives from Synasia；Voranol 4000
It is poly- (expoxy propane) of molecular weight 4000, commercially available from Dow；2- ethyls 4-methylimidazole is purchased from Aldrich Chemical；
" DMTA " represents differential Mechanical Thermal Analysis；" ARES " represents advanced Rheometric Expansion System.
In the following examples, the Tg of cured product is measured by DMTA.DMTA is performed using ARES solid-states analyzer.Will
Substantially 2.5 " x of x 0.5 " 0.125 " Rectangular samples insertion solid-state fixture in and torsional load vibrated.Record shearing storage
Can modulus G ', shearing loss modulus G " and tan δ (G "/G ').Use 1Hz angular frequency.Sample is carried out on dynamic temperature step
Rise, 300 DEG C are risen to from room temperature (about 28 DEG C) with 3 DEG C/min.
According to ASTM D-5045, the fracture toughness of compact tension specimen sample dimensional measurement cured product is used.
Embodiment 1
DER 383 (49.42g), MTHPA (45.48g), Acclaim 8200 (5g) are put into 250mL R.B. flasks,
And mixed at 70 DEG C, obtain uniform mixture.Add catalyst (2 ethyls -4-methylimidazole, 1g) and be sufficiently stirred
3 minutes.The solution is deaerated by centrifuging, pours into and solidifies in mould and in an oven under high temperature.The solidification scheme used is
At 90 DEG C 4 hours at 2 hours, 150 DEG C, room temperature (about 25 DEG C) is subsequently cooled to.
The Tg of the cured product (thermosets) of gained is 138 DEG C, and the fracture toughness of the cured product is
1.2MPa/m1/2。
Embodiment 2
NMA (52.5g), Acclaim 8200 (30g) are put into 250mL round-bottomed flasks, and mixed at 70 DEG C, is obtained
To uniform mixture.Add catalyst (2-ethyl-4-methylimidazole, 1.8g) and be sufficiently stirred 3 minutes.Add thereto
D.E.R.383 and SYNA EPOXY 21 (30: 70 ratio) admixture, and (about 25 DEG C) are sufficiently stirred at room temperature, are obtained
Even solution.The solution is deaerated by centrifuging, pours into and solidifies in mould and in an oven under high temperature.The solidification scheme used
It is at 90 DEG C at 2 hours, 150 DEG C 2 hours at 2 hours, 200 DEG C, is subsequently cooled to room temperature.
The Tg of the cured product (thermosets) of gained is 232 DEG C, and the fracture toughness of the cured product is
0.84MPa/m1/2。
Embodiment 3
NMA (24.02g), the polypropylene of Acclaim 8200 (7.5g) are put into 250mL round-bottomed flasks, and in 70 DEG C of mixing
Together, uniform mixture is obtained.Add catalyst (2-ethyl-4-methylimidazole, 0.45g) and be sufficiently stirred 3 minutes.To
SYNA EPOXY 21 (18.48g) are wherein added, and are sufficiently stirred at room temperature, obtain uniform solution.The solution is led to
Centrifugation degassing is crossed, pours into and solidifies in mould and in an oven under high temperature.The solidification scheme used is at 90 DEG C at 2 hours, 150 DEG C
2 hours at 2 hours, 200 DEG C, room temperature (about 25 DEG C) is subsequently cooled to.
The Tg of the cured product (thermosets) of gained is 259 DEG C, and the fracture toughness of the cured product is
0.84MPa/m1/2。
Embodiment 4
D.E.R.383 (57g, 0.314 equivalent), SD-1731 (33g, 0.314 equivalent) and 75g acetone are added into 500mL circles
Bottom flask.The mixture is sufficiently stirred, obtains uniform solution.Acetone is removed by rotary evaporation, added into solution
Acclaim 8200 (10g) and catalyst (1wt%, 2-ethyl-4-methylimidazole), and stir 5 minutes, uniformly to be glued
Property liquid.The viscous liquid is subsequently poured into mould, and is solidified at high temperature in an oven.The solidification scheme used is 90 DEG C
4 hours at lower 2 hours, 150 DEG C, room temperature (about 25 DEG C) is subsequently cooled to.
Embodiment 5
D.E.R.383 (48.6g) and DL-50 (13.65g, 0.267 equivalent) is added into 8 ounce glass jars and is sufficiently mixed
To obtain uniform clarified solution.The mixture that Acclaim 8200 (5g) is added in bottle, and be sufficiently mixed.The clarification of gained
Solution is deaerated by centrifuging, and is poured into mould and is solidified in an oven with following program curing：80 DEG C (2 hours), then 150
DEG C (3 hours).
Comparative examples A
This Comparative examples A uses the identical program of example 1 above, and Voranol 4000 replaces Acclaim 8200 to be used as increasing
Tough dose.The Tg of the cured product of gained is 133 DEG C, and the fracture toughness of the cured product is 1.3MPa/m1/2。
Comparative example B
This comparative example B uses the identical program of example 1 above, simply without using toughener.The cured product of gained
Tg is 137 DEG C, and the fracture toughness of the cured product is 0.5MPa/m1/2。
Comparative example C
This comparative example C uses the identical program of example 2 above, simply without using toughener.The cured product of gained
Tg is 232 DEG C, and the fracture toughness of the cured product is 0.4MPa/m1/2。
Comparative Example D
This Comparative Example D uses the identical program of example 3 above, simply without using toughener.The cured product of gained
Tg is 244 DEG C and the cured product is very brittle.
Lower Table I is summarised in different epoxy resin-anhydride systems using the high-molecular-weight poly (epoxy third of the present invention
Alkane) polyalcohol the advantages of.
Table I
Claims (7)
1. a kind of curable composition epoxy resin, it includes (a) at least one epoxy resin；(b) it is at least one selected from extremely
The curing agent of a kind of acid anhydrides, at least one linear phenol-aldehyde resin, at least one amine or its mixture less；At least one tool (c)
There is high-molecular-weight poly (expoxy propane) polyalcohol toughener of following chemical constitution；
The number-average molecular weight of wherein described poly- (expoxy propane) polyalcohol toughener be 7,000 to
16,000, and the Tg of wherein final cured product is 70 DEG C to 265 DEG C.
2. the composition of claim 1, wherein the epoxy resin includes liquid epoxies.
3. the composition of claim 1, wherein the epoxy resin includes cycloaliphatic resin.
4. the composition of claim 1, wherein the epoxy resin includes novolac epoxy resin.
5. the composition of claim 1, wherein the polyalcohol includes high-molecular-weight poly (expoxy propane) glycol, high-molecular-weight poly
(PPOX) triol or its mixture.
6. the composition of claim 1, wherein the concentration of the epoxy resin accounts for 30 percentage by weights to 90 percentage by weights.
7. the composition of claim 1, wherein the concentration of poly- (expoxy propane) the polyalcohol toughener accounts for 1 percentage by weight extremely
25 percentage by weights.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31696210P | 2010-03-24 | 2010-03-24 | |
| US61/316,962 | 2010-03-24 | ||
| PCT/US2011/000522 WO2011119216A2 (en) | 2010-03-24 | 2011-03-22 | Epoxy resin compositions comprising poly ( propylene oxide) polyol as toughening agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102884100A CN102884100A (en) | 2013-01-16 |
| CN102884100B true CN102884100B (en) | 2018-02-06 |
Family
ID=44511820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180020459.2A Active CN102884100B (en) | 2010-03-24 | 2011-03-22 | Include the composition epoxy resin of poly- (expoxy propane) polyalcohol as toughener |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US8927677B2 (en) |
| EP (1) | EP2550310B1 (en) |
| KR (1) | KR20130062915A (en) |
| CN (1) | CN102884100B (en) |
| BR (1) | BR112012023949A2 (en) |
| PL (1) | PL2550310T3 (en) |
| WO (1) | WO2011119216A2 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013096635A2 (en) | 2011-12-22 | 2013-06-27 | Dow Global Technologies Llc | Epoxy elastomer compositions |
| US20150210846A1 (en) * | 2012-04-27 | 2015-07-30 | Dow Global Technologies Llc | Curable epoxy resin compositions and composites made therefrom |
| WO2014062903A1 (en) * | 2012-10-19 | 2014-04-24 | Dow Global Technologies Llc | Polymer particle dispersions with polyols |
| BR112015008431A2 (en) * | 2012-10-19 | 2017-07-04 | Dow Global Technologies Llc | curable resin composition, process for preparing a curable resin composition, cured resin composition and article |
| KR20150131015A (en) * | 2013-03-15 | 2015-11-24 | 블루 큐브 아이피 엘엘씨 | Toughened epoxy thermosets containing core shell rubbers and polyols |
| EP3052540B1 (en) * | 2013-10-01 | 2017-11-15 | Basf Se | Multi-component epoxy resin composition |
| EP3161037B1 (en) * | 2014-06-26 | 2018-08-15 | Dow Global Technologies LLC | Fast curing resin compositions, manufacture and use thereof |
| WO2016060923A1 (en) * | 2014-10-13 | 2016-04-21 | Dow Global Technologies Llc | Epoxy composition containing acrylate based toughening agent |
| US9296915B1 (en) | 2015-04-10 | 2016-03-29 | Dow Global Technologies Llc | Toughened arylcyclobutene polymers |
| WO2017179653A1 (en) | 2016-04-13 | 2017-10-19 | 株式会社カネカ | Toughened epoxy resin composition |
| DE102016006910A1 (en) * | 2016-06-08 | 2017-12-14 | Hexion GmbH | Composition containing a polymer based on epoxy compounds |
| US11292871B2 (en) | 2017-06-09 | 2022-04-05 | Hexion Inc. | Epoxy resin systems for composites |
| KR102161451B1 (en) * | 2019-07-12 | 2020-10-06 | 주식회사 삼양사 | Anhydrous alcohol-based urethane-modified polyol composition and toughening agent for an epoxy resin comprising the same, and epoxy resin composition comprising the toughening agent |
| EP3825115A1 (en) * | 2019-11-22 | 2021-05-26 | Henkel AG & Co. KGaA | Peo-ppo-peo triblock copolymers as additives for epoxy anhydride systems |
| CN116535820B (en) * | 2023-07-06 | 2023-09-29 | 道生天合材料科技(上海)股份有限公司 | Epoxy anhydride resin system material for pultrusion as well as preparation method and application thereof |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3018262A (en) | 1957-05-01 | 1962-01-23 | Shell Oil Co | Curing polyepoxides with certain metal salts of inorganic acids |
| US4052349A (en) * | 1975-10-28 | 1977-10-04 | Olin Corporation | Epoxy composition containing a chlorine-containing polyol and its use as an adhesive |
| JPS5628253A (en) * | 1979-08-17 | 1981-03-19 | Mitsubishi Electric Corp | Epoxy resin composition for powder coating |
| US4497945A (en) * | 1983-06-20 | 1985-02-05 | General Motors Corporation | Tough epoxy polymers formable by reaction injection molding |
| US5135993A (en) | 1990-09-11 | 1992-08-04 | Dow Corning Corporation | High modulus silicones as toughening agents for epoxy resins |
| GB9411367D0 (en) | 1994-06-07 | 1994-07-27 | Ici Composites Inc | Curable Composites |
| US5696225A (en) * | 1996-02-28 | 1997-12-09 | Arco Chemical Technology, L.P. | Process for making high-performance polyetherester resins and thermosets |
| US6613839B1 (en) | 1997-01-21 | 2003-09-02 | The Dow Chemical Company | Polyepoxide, catalyst/cure inhibitor complex and anhydride |
| US6153719A (en) | 1998-02-04 | 2000-11-28 | Lord Corporation | Thiol-cured epoxy composition |
| US6632893B2 (en) | 1999-05-28 | 2003-10-14 | Henkel Loctite Corporation | Composition of epoxy resin, cyanate ester, imidazole and polysulfide tougheners |
| US6572971B2 (en) | 2001-02-26 | 2003-06-03 | Ashland Chemical | Structural modified epoxy adhesive compositions |
| US6632860B1 (en) | 2001-08-24 | 2003-10-14 | Texas Research International, Inc. | Coating with primer and topcoat both containing polysulfide, epoxy resin and rubber toughener |
| GB0212062D0 (en) | 2002-05-24 | 2002-07-03 | Vantico Ag | Jetable compositions |
| US7163973B2 (en) | 2002-08-08 | 2007-01-16 | Henkel Corporation | Composition of bulk filler and epoxy-clay nanocomposite |
| US7056978B2 (en) * | 2002-11-06 | 2006-06-06 | National Starch And Chemical Investment Holding Corporation | Toughened epoxy-anhydride no-flow underfill encapsulant |
| US6887574B2 (en) | 2003-06-06 | 2005-05-03 | Dow Global Technologies Inc. | Curable flame retardant epoxy compositions |
| JP2006063135A (en) * | 2004-08-25 | 2006-03-09 | Dainippon Ink & Chem Inc | Ultraviolet-curing resin composition |
| US7923073B2 (en) | 2004-11-10 | 2011-04-12 | Dow Global Technologies Llc | Amphiphilic block copolymer-toughened epoxy resins and electrical laminates made therefrom |
| US8048819B2 (en) | 2005-06-23 | 2011-11-01 | Momentive Performance Materials Inc. | Cure catalyst, composition, electronic device and associated method |
| TW200728341A (en) * | 2005-09-13 | 2007-08-01 | Huntsman Adv Mat Switzerland | Photocurable compositions for preparing ABS-like articles |
| US7435982B2 (en) | 2006-03-31 | 2008-10-14 | Energetiq Technology, Inc. | Laser-driven light source |
| BRPI0924015A2 (en) * | 2009-04-21 | 2016-01-26 | Dow Global Technologies Llc | curing agent composition, curable composition and thermosetting product |
-
2011
- 2011-03-22 CN CN201180020459.2A patent/CN102884100B/en active Active
- 2011-03-22 WO PCT/US2011/000522 patent/WO2011119216A2/en active Application Filing
- 2011-03-22 US US13/636,282 patent/US8927677B2/en active Active
- 2011-03-22 PL PL11713534T patent/PL2550310T3/en unknown
- 2011-03-22 EP EP11713534.3A patent/EP2550310B1/en active Active
- 2011-03-22 KR KR1020127027459A patent/KR20130062915A/en not_active Application Discontinuation
- 2011-03-22 BR BR112012023949A patent/BR112012023949A2/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| BR112012023949A2 (en) | 2017-08-08 |
| CN102884100A (en) | 2013-01-16 |
| PL2550310T3 (en) | 2018-10-31 |
| US20130131217A1 (en) | 2013-05-23 |
| WO2011119216A3 (en) | 2012-01-05 |
| KR20130062915A (en) | 2013-06-13 |
| EP2550310B1 (en) | 2018-05-02 |
| US8927677B2 (en) | 2015-01-06 |
| EP2550310A2 (en) | 2013-01-30 |
| WO2011119216A2 (en) | 2011-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102884100B (en) | Include the composition epoxy resin of poly- (expoxy propane) polyalcohol as toughener | |
| JP5259397B2 (en) | Reinforced composition | |
| US4798761A (en) | Epoxy resin compositions for use in low temperature curing applications | |
| RU2574054C2 (en) | Epoxy resin-based curable compositions and composite materials obtained therefrom | |
| SG174631A1 (en) | Curable flame retardant epoxy resin compositions | |
| TW200936683A (en) | High Tg epoxy systems for composite application | |
| TW200918593A (en) | Thermoset dampener material | |
| TW200951175A (en) | Use of filler that undergoes endothermic phase transition to lower the reaction exotherm of epoxy based compositions | |
| WO2013115152A1 (en) | Epoxy resin composition and fiber-reinforced composite material | |
| WO2014149074A1 (en) | Toughened epoxy thermosets containing core shell rubbers and polyols | |
| CN112105671B (en) | Cycloaliphatic amines for epoxy formulations: novel curing agents for epoxy systems | |
| US9845387B2 (en) | Toughened epoxy thermosets containing core shell rubbers and polyols | |
| JPS5927916A (en) | Epoxy resin composition and workability improvement therefor | |
| CN105531316A (en) | A curable epoxy resin composition | |
| WO2003000798A1 (en) | Thermosetting resin composition, process for producing the same, and suspension-form mixture | |
| JPS58138729A (en) | Thermosetting molding composition | |
| TW201434950A (en) | Curable epoxy resin compositions | |
| AU610959B2 (en) | Epoxy resin compositions for use in low temperature curing applications | |
| JPS59164321A (en) | Epoxy resin composition | |
| JP2003252943A (en) | Thermosetting resin composition and its cured product | |
| JPS5966418A (en) | Epoxy resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20170728 Address after: michigan Applicant after: BLUE CUBE INTELLECTUAL PROPERTY CO., LTD. Address before: michigan Applicant before: Dow Global Technologies Inc. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |